CN101657758A - Alkaline-resistant negative photoresist for silicon wet-etch without silicon nitride - Google Patents
Alkaline-resistant negative photoresist for silicon wet-etch without silicon nitride Download PDFInfo
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- CN101657758A CN101657758A CN200880012312A CN200880012312A CN101657758A CN 101657758 A CN101657758 A CN 101657758A CN 200880012312 A CN200880012312 A CN 200880012312A CN 200880012312 A CN200880012312 A CN 200880012312A CN 101657758 A CN101657758 A CN 101657758A
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- silane
- polymkeric substance
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/108—Polyolefin or halogen containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/115—Cationic or anionic
Abstract
A removable build box for a three dimensional printer comprises a build box tray defining a build chamber for part assembly and a material feed chamber for supplying powder material to the build chamber. The build and feed chambers have lower piston stops. A build chamber piston engages with the build chamber and with the build chamber piston stops at a lowermost position. A feed chamber piston engages with the feed chamber and with the feed chamber piston stops at a lowermost position. A quick connection coupling is between the build chamber piston and a build chamber z-axis actuator configured to move the build chamber piston when connected thereto. A quick connection coupling is between the feed chamber piston and a feed chamber z-axis actuator configured to move the feed chamber pistonwhen connected thereto. The build box tray may be easily removed from the three dimensional printer.
Description
Background of invention
Invention field
The present invention relates to be used to make the new photoresist of microelectronic component (microelectronic component that for example is used for microelectromechanical-systems (MEMS)).
DESCRIPTION OF THE PRIOR ART
Be everlasting in the silicon etch process use on the silicon substrate thin (100-300 nanometer) silicon nitride or silica dioxide coating as the mask of pattern etched or as passivation layer with the sealing active electric network.In the prior art, mainly by using try and error method that the etching protective finish or the mask that are used for the MEMS manufacture process are selected, reason is not have general protective finish on the market.The MEMS technologist often use etchant to the etching selectivity of various materials as guidance.The etch-rate of silicon nitride film is more much lower than silicon, so used silicon nitride film as KOH or TMAH body phase silicon etched protective layer or hard mask.The etch-rate of silicon dioxide is greater than silicon nitride.Therefore, silicon dioxide only is used as very short time etched protective/mask layer.According to report, gold (Au), chromium (Cr) and boron (B) have also been used in some cases.(hard-baked) photoresist that excessively cures that has used patterning not is as mask, but etching takes place in alkaline solution easily for they.Also polymethylmethacrylate is estimated as the etching mask of KOH.But, because the saponification of ester group, when the masking period of finding this polymkeric substance 165 minutes during from 60 ℃ sharply are reduced to 90 ℃ 15 minutes.
Do not consider selected protective finish or mask, must will treat that the photoresist layer of patterning is applied to protective finish or mask, thus can be with design transfer to following base material.But this can only carry out after having used protective finish or mask, therefore need the time and become to use originally protective finish or mask, and this protective finish of etching afterwards or mask, this protective finish or mask are very difficult to remove.
Summary of the invention
The present invention replaces the mask or the protective finish of prior art by the photosensitive coating system used of rotation is provided, and does not need extra photoresist in this system, thereby has overcome these problems.The erosion of corrosion or other form in order to avoid take place in system protection device element of the present invention during the deep etching process of using strong lye solution.
The invention provides the photosensitive composition that is suitable as protective seam.Said composition comprises first polymkeric substance, second polymkeric substance and photo-acid agent (photoacid generator) blend in dicyandiamide solution.First polymkeric substance comprises the monomer that contains cinnamic monomer and contain vinyl cyanide, and second polymkeric substance comprises the monomer that contains epoxy.
In one embodiment, second polymkeric substance also comprises the monomer that contains phenols, this phenolic group can with epoxide group on the same monomer, can with epoxide group on different monomers or can be both potpourris.The present invention also provides in conjunction with prime coat (primer layer) thereby uses these photosensitive compositions to form the method for microelectronic structures.
Brief Description Of Drawings
Fig. 1 is the side cross-sectional view according to front body structure of the present invention; And
Fig. 2 is the planimetric map of front body structure shown in Figure 1.
The detailed description of the preferred embodiment for the present invention
More particularly, these optimum system choosings comprise the prime coat that is applied to the microelectronic substrates surface, and the photosensitive layer that is applied to prime coat.
Prime coat
Preferred prime coat is formed by the prime coat composition, and said composition comprises the silane that is dispersed or dissolved in the dicyandiamide solution.Aromatic series and organosilane are the particularly preferred silane that is used for prime coat of the present invention.And preferably each compound molecule of this silane or each polymer repeat unit comprise at least one (more preferably 2-3) and can form covalent bond with the epoxide group reaction and make the very strong group of adhesion with silicon substrate.A kind of preferred this type of group is an amine groups.
Preferred silane comprises aminoalkoxy silane, preferably C roughly
1To C
8Alkoxy more preferably is C roughly
1To C
4Alkoxy is more preferably roughly C
1To C
3Alkoxy.More preferably this aminoalkoxy silane is the aminoalkyl alkoxy silane, preferably C roughly
1To C
8Alkyl more preferably is C roughly
1To C
4Alkyl is more preferably roughly C
1To C
3Alkyl.Also preferred phenyl amino alkylalkoxy silane.Some above-mentioned examples comprise TSL 8330, aminopropyltriethoxywerene werene, N-phenyl amino propyl trimethoxy silicane, N-phenyl amino propyl-triethoxysilicane, the 3-glycidoxypropyltrime,hoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, and 3-sulfydryl propyl group-trimethoxy silane.
Other preferred silane comprises phenyl silane, phenyltrimethoxysila,e for example, phenyl trichlorosilane, phenyl triethoxysilane, phenyl triacetoxysilane; Diphenyl silane, dimethoxydiphenylsilane for example, diphenyl dichlorosilane; And diphenyl silanodiol.Most preferred silane comprises 2-phenylethyl trialkoxy silane, right/-the chlorphenyl trimethoxy silane, right/-the bromophenyl trimethoxy silane, (right/-chloromethyl) phenyltrimethoxysila,e, 2-(right/-methoxyl) the phenylethyl trimethoxy silane, 2-(right/-chloromethyl) the phenylethyl trimethoxy silane, 3,4-dichlorophenyl trichlorosilane, 3-phenoxy propyl trichlorosilane, 3-(N-phenyl amino) propyl trimethoxy silicane, and 2-(diphenylphosphino) ethyl triethoxysilane.
Some are preferred for silane of the present invention and can also represent by following general formula:
Wherein:
Wherein:
Each i, j and k are independently selected from 0 and 1, if among i and the j one be 1, then another is 0;
Each R
4Be independently selected from hydrogen, halogen, C
1-C
8(preferred C
1-C
4) alkyl, C
1-C
8(preferred C
1-C
4) alkoxy, C
1-C
8(preferred C
1-C
4) haloalkyl, amino and C
1-C
8(preferred C
1-C
4) alkyl amino;
Each R
5Be independently selected from C
1-C
8(preferred C
1-C
4) aliphatic group;
Each R
6Be independently selected from hydrogen and haloalkyl (preferred C
1-C
8, more preferably C
1-C
4);
Each X is independently selected from halogen, hydroxyl, C
1-C
4Alkoxy and C
1-C
4Carboxyl;
Y is selected from oxygen and sulphur;
Z is selected from nitrogen and phosphorus;
Each d is independently selected from 0 and 1.
A kind of effective prime coat composition is the potpourri of diphenyl dialkoxy silicane (for example dimethoxydiphenylsilane) and phenyl trialkoxy silane (for example phenyltrimethoxysila,e) according to the present invention, perhaps even be more preferably diphenyl silanodiol and the phenyltrimethoxysila,e potpourri in the solution of 1-methoxyl-2-propyl alcohol or 1-propoxyl group-2-propyl alcohol and about 10-60 weight % water.The photosensitive layer of poly-for comprising (styrene-copolymerization-vinyl cyanide) polymkeric substance, especially effectively the prime coat composition is the alcohol solution that comprises about 0.1-1.0 weight % (preferably about 0.25-0.5 weight %) diphenyl silanodiol and about 0.1-1.0 weight % (preferably about 0.25-0.5 weight %) phenyltrimethoxysila,e.During heating, diphenyl silanodiol and phenyl silane triol (hydrolysate of phenyltrimethoxysila,e) condensation forms siloxane bond, builds three-dimensional silicone coating on base material.
Another kind of preferred silane has following general formula:
Wherein:
Each R
7Be independently selected from hydrogen, halogen, C
1-C
8(preferred C
1-C
4) alkyl, C
1-C
8(preferred C
1-C
4) alkoxy, C
1-C
8(preferred C
1-C
4) haloalkyl, amino and C
1-C
8(preferred C
1-C
4) alkyl amino;
Each R
8Be independently selected from C
1-C
8(preferred C
1-C
4) aliphatic group.
Silane with this structure can not only be with to contain cinnamic multipolymer compatible, and can with ester, benzyl chloride and/or epoxide group reaction, they are excellent adhesion promoters.A kind of particularly preferred silane in this general formula scope is:
This silane is the 3-[N-phenyl amino] propyl trimethoxy silicane (as mentioned above), can buy with Ji Lesite company (Lancaster Synthesis and Gelest Corporation) from Lancaster is synthetic.
In the prime coat composition, be the benchmark of 100 weight % in total weight of solids in the prime coat composition, the content of this silane should be about 0.1-3 weight %, preferably is about 0.2-2 weight %, is more preferably 0.5-1 weight %.
The boiling point of the dicyandiamide solution that uses in the prime coat composition should be about 100-220 ℃, preferably is about 140-180 ℃.General assembly (TW) in the prime coat composition is the benchmark of 100 weight %, and the content of solvent for use system should be about 30-99.9 weight %, preferably is about 40-80 weight %.Preferred dicyandiamide solution comprises and is selected from following solvent: methyl alcohol, ethanol, isopropyl alcohol, butanols, 1-methoxyl-2-propyl alcohol, glycol monoethyl ether, propylene glycol propyl ether, 1-propoxyl group-2-propyl alcohol, and their potpourri.One preferred embodiment in, be the benchmark of 100 weight % in the general assembly (TW) of prime coat composition, the water cut in the dicyandiamide solution is about 20-60 weight %, preferably is about 40-60 weight %.
The prime coat composition also can comprise catalyzer.Appropriate catalyst comprises any inorganic or organic acid (for example hydrochloric acid, sulfuric acid, phosphoric acid, acetate) or inorganic or organic base (for example potassium hydroxide, TMAH, ammonia, amine).In the prime coat composition, be the benchmark of 100 weight % in the total weight of solids in the prime coat composition, the content of catalyzer preferably is about 0.01-0.5 weight %, more preferably about being 0.1-0.3 weight %, is more preferably 0.02-0.03 weight %.
At last, prime coat also can comprise many optional members, for example surfactant.In one embodiment, the surfactant that can add about 100-400ppm for example FC4430 (obtaining) or Triton X-100 (obtaining) by 3M company by 3M company to make flawless even prime coat layer.
Photosensitive layer
Photosensitive layer is formed by a kind of composition, and said composition comprises at least two kinds of polymkeric substance that are dispersed or dissolved in the dicyandiamide solution.First polymkeric substance in these two kinds of polymkeric substance preferably comprises the styrene monomer of repetition and the multipolymer of acrylonitrile monemer.
Preferred styrene monomer has following general formula:
Preferred acrylonitrile monemer has following general formula:
At above each general formula (I) with (II):
Each R
1Be independently selected from hydrogen and C
1-C
8(preferred C
1-C
4) alkyl;
Each R
2Be independently selected from hydrogen, C
1-C
8(preferred C
1-C
4) alkyl and C
1-C
8(preferred C
1-C
4) alkoxy.
First polymkeric substance preferably comprises the monomer (I) of about 50-90 weight %, more preferably about the monomer (I) of 60-80 weight %, the more preferably from about monomer of 70-75 weight % (I).First polymkeric substance preferably comprises the monomer (II) of about 10-50 weight %, more preferably about the monomer (II) of 20-40 weight %, the more preferably from about monomer of 25-30 weight % (II).More than each percent by weight be that general assembly (TW) in first polymkeric substance is the benchmark of 100 weight %.
The weight-average molecular weight of preferred first polymkeric substance is about 10000-80000 dalton, more preferably about being 20000-60000 dalton, is more preferably 30000-50000 dalton.
Also can there be demonomerization (I) and (II) in addition monomer when needing in first polymkeric substance.When having other monomer, be the benchmark of 100 weight % in the general assembly (TW) of first polymkeric substance, monomer in the polymkeric substance (I) and weight sum (II) preferably are at least about 60 weight %, are more preferably 70-90 weight %.Thereby comprising having, the example of other suitable monomer can between two layers, realize the monomer of the functional group that chemical combination combines with the radical reaction in the prime coat.These monomers can be, for example haloalkyl (for example benzyl chloride, methacrylic acid 2-chloroethene ester), ester (methacrylate, acrylate, maleate, fumarate, isocyanates) or anhydride functional group, they easily with prime coat in functional group's (for example hydroxyl, amino or epoxy ethyl) of existing react.
In the photosensitive layer composition, be the benchmark of 100 weight % in the general assembly (TW) of solid in the photosensitive layer composition, the content of first polymkeric substance should be about 30-70 weight %, preferably is about 50-65 weight %.
Second polymkeric substance that exists in the said composition comprises the repeated monomer that each monomer has one or more epoxide groups, and preferably this polymkeric substance comprises the monomer that each monomer has at least two epoxide groups.A kind of preferred embodiment in, this second polymkeric substance also comprises the monomer that contains phenolic group.This phenolic group can be positioned on the independent monomer, perhaps can be included on the identical monomer with epoxide group.
Second polymkeric substance preferably comprises the epoxide group of about 15-30 weight %, the more preferably from about epoxide group of 20-25 weight %.In having the embodiment of phenolic group, this polymkeric substance preferably comprises the phenolic group of about 40-70 weight %, the more preferably from about phenolic group of 50-60 weight %.More than each percent by weight be the benchmark of 100 weight % in the general assembly (TW) of second polymkeric substance.
The weight-average molecular weight of preferred second polymkeric substance is about 300-10000 dalton, more preferably about being 500-5000 dalton, is more preferably 1000-2000 dalton.
The preferred polymers that is used as second polymkeric substance in photosensitive composition comprises and is selected from following polymkeric substance: (for example DEN 431 for epoxy phenol novolac resin (epoxy phenol novolac resins), DOW Chemical (Dow Chemical)), (for example DER 353 for epoxy bisphenol-A/F resin, DOW Chemical), (for example ECN 1299 for cresol novolac epoxy varnish gum (epoxy cresol novolac resins), vapour Ba Jirui (CibaGeigy)), (for example EPON 825 for the epoxy bisphenol a resin, DOW Chemical), epoxy bisphenol-A phenolic varnish gum (epoxy bisphenol A novolac resins) (EPON SU-8, and their potpourri DOW Chemical).
Also can have the monomer except that the monomer that contains epoxy and/or phenolic group when needing in second polymkeric substance, prerequisite is to reach epoxy quantity discussed above.The example of other suitable monomer comprises the above example that first polymkeric substance is discussed.
In the photosensitive layer composition, be the benchmark of 100 weight % in the general assembly (TW) of solid in the photosensitive layer composition, the content of second polymkeric substance should be about 20-60 weight %, preferably is about 25-40 weight %.
Photosensitive composition will also comprise photo-acid agent (PAG).With actinic radiation for example ultraviolet light expose to the sun when penetrating PAG, it produces strong acid or super acid.The example of suitable PAG comprises and is selected from following example: the hexafluoro-antimonic acid triaryl matte, and hexafluorophosphoric acid triaryl matte (for example UVI 6976, DOW Chemical), hexafluoro-antimonic acid diaryl iodine, hexafluorophosphoric acid diaryl iodine,
Wherein:
Each R
3Be independently selected from C
3H
7, C
8H
17, CH
3C
6H
4And camphor.General formula (IV) and PAG (V) cling to specialty chemical corporation (Ciba Specialty Chemical) by vapour and sell, and CGI 13XX series and CGI 26X series are arranged respectively.
In the photosensitive composition, be the benchmark of 100 weight % in the general assembly (TW) of solid in the photosensitive composition, the content of PAG should be about 2-10 weight %, preferably is about 5-8 weight %.
The boiling point of the dicyandiamide solution that uses in the photosensitive composition should be about 120-200 ℃, preferably is about 130-180 ℃.General assembly (TW) in photosensitive composition is the benchmark of 100 weight %, and the consumption of dicyandiamide solution should be about 70-95 weight %, preferably is about 80-90 weight %.Preferred dicyandiamide solution comprises and is selected from following solvent: methyl isoamyl ketone, two (ethylene glycol) dimethyl ether, propylene glycol methyl ether acetate, ethyl lactate, cyclohexanone and their potpourri.
Application process
With silane and arbitrarily other components dissolved in the bottoming agent dicyandiamide solution, form silane.With about 500-5000rpm, preferably the rotating speed of about 1000-3000rpm is applied in said composition rotation on the base material, time of application is about 30-90 second, preferably is about 60 seconds then.Cure about 60-180 second (preferred about 60 seconds) about 60-110 ℃ temperature then, cure about 60-180 second (preferred about 60 seconds) at about 150-280 ℃ again, make silane molecule be condensed into continuous film 14, the surface hydroxyl that exists on this film and the typical microelectronic substrates combines.That is to say that the silanol groups reaction that exists in the silane of hydrolysis and the siliceous substrates is also by the condensation self-crosslinking.The average thickness (measuring at 5 differences by ellipsometer) of preferred this prime coat less than about 50 nanometers, is more preferably the 20-30 nanometer.
For photosensitive layer, first and second polymkeric substance, PAG and arbitrarily other components all be dissolved in the dicyandiamide solution and (or individually form multiple solution or dispersion with corresponding solvent, mix then), and with about 1000-5000rpm, preferably the rotating speed of about 1000-2000rpm is spin-coated on the base material, the spin coating time is about 30-90 second, preferably is about 60 seconds.Cure about 60-180 second (preferred about 120 seconds) about 100-120 ℃ temperature then, form photosensitive layer 16.Common telomerized polymer solid level and spin coating condition, thereby realize about 500-3000 nanometer, the preferred average coating thickness of about 1000-2000 nanometer (the usefulness ellipsometer is measured at 5 differences) after curing, this depends on the required level of coverage of device topography on the base material.Amine on the silane of the epoxy in the photosensitive layer polymkeric substance or other reactive group and prime coat or other reactive group advantageously generate covalent bond.
Then by with the wavelength of about 150-500 nanometer (for example about 248 nanometers or about 365 nanometers), preferably with about 500 dosage of Jiao/square centimeters in the least, photosensitive layer is carried out ultraviolet light expose to the sun and penetrate, make its imaging.Preferably penetrate the back and cured this coating about 2 minutes with about 110-130 ℃ exposing to the sun, and with solvent develop about 2 minutes.At last, cured coating about 3 minutes with about 200-250 ℃.
Exposing to the sun to penetrating with light makes PAG produce acid, and this acid takes place crosslinked at the epoxide group that causes in the photosensitive layer during curing after penetrating that exposes to the sun.Crosslinked epoxide group will have following structure:
Therefore, the photosensitive layer of curing will comprise the crosslinked epoxide group of many these classes, and some may untouched not moving (that is, unreacted) epoxide group.
Expose to the sun penetrate the district in typical solvent developers (for example propylene glycol methyl ether acetate, methyl isoamyl ketone, ethyl lactate and ethyl acetoacetate), become insoluble substantially (for example, solvable less than about 1 weight %, preferably solvable less than about 0.05%, more preferably from about 0% is solvable).Not exposing to the sun to penetrating to distinguish keeps dissolving in these developers, therefore removes during developing easily, thereby form opening 18a in photosensitive layer 16.Opening 18a is limited by edge 20a and 20b, has corresponding end point 22a and 22b separately.
Do not need extra etching step (that is, during the base material etching step) just can easily shift pattern,, in protective seam 14, form opening 18b (limiting) by sidewall 24a and 24b to remove protective seam 14.During same etching step, this design transfer forms opening 26 in base material 12 to base material 12 then.Opening 18c has height " H ", can be through hole, contact hole, groove, space etc.
As shown in Figure 1, the width of opening 18b is greater than the width of 18a, and reason is that " recessed cutting (undercutting) " takes place during etching process usually.Implement the present invention and will be formed on the protective layer system that has little or no recessed cutting " U " during the etching process.That is to say, about 3 hours of etching in the KOH aqueous solution of about 75-85 ℃ temperature, about 30-35 weight % (perhaps even about 4 hours) afterwards, recessed cut percentage will less than about 20%, preferably less than about 15% even be more preferably less than about 10%.
By measuring (for example using confocal microscope) distance " U ", determine recessed cutting from end point 22a to sidewall 24a and protection against light sensitivity layer 16 contact point.Determine the recessed percentage of cutting according to following formula then:
And protection system of the present invention will experience or not experience fully the etchant infiltration hardly during etching process.Therefore; with about 3 hours of about 75-85 ℃ temperature, the etching of about 30-35 weight %KOH aqueous solution (perhaps even about 4 hours) time; observe at the microscopically of 10 times of amplifications, the pinhole number of protective seam 16 every square centimeter of base materials of the present invention will be less than about 0.1, preferably less than about 0.05.The prior art photosensitive layer is dissolved among the KOH usually quickly, therefore requires to exist for example silicon nitride layer of independent protective seam.
Embodiment
Following examples the preferred method of the present invention of giving chapter and verse.But should be appreciated that provide these embodiment in the mode that illustrates, any embodiment should not regard the restriction to overall range of the present invention as.
Embodiment 1
The preparation of bottoming agent solution
In order to prepare bottoming agent solution, (the Ji Lesite company (Gelest, Morrisville, PA)) that derives from Pennsylvania Mo Siwei is dissolved in 77.50 gram propylene glycol propyl ether (PnP with 2.04 gram N-phenyl amino propyl trimethoxy silicanes; Derive from (the General Chemical of general chemical company of New Jersey Pai Ruisipi, Parsippany, NJ)), 120.14 gram deionized waters, 0.51 gram acetate (derive from (Aldrich of A Deruiqi company of Milwaukee, the state of Wisconsin, Milwaukee, and 0.03 gram FC-4430 (surfactant WI)), (3M, St.Paul is MN) in) the potpourri to derive from the 3M company in Sao Paulo, the Minnesota State.This solution of magnetic agitation was above 2 hours.Filter by 0.1 micron film filtrator then.
Embodiment 2
The copolymer solution preparation
By (the Baeyer u s company (Bayer USA, Pittsburgh, PA)) that derives from the Pennsylvania Pittsburgh is dissolved in 595.0 gram propylene glycol methyl ether acetate (PGMEA with 150.1 gram polystyrene-copolymerization-polyacrylonitrile multipolymers; Derive from general chemical company (General Chemical, Parsippany, NJ)) and the 255.0 gram ethyl acetoacetate (EAA of New Jersey Pai Ruisipi; Derive from Kansas City, the Kansas State Kazakhstan Cross Co. (Harcros, Kansas City, KS) in) the potpourri, the preparation copolymer solution.
Embodiment 3
The photo-acid agent formulations prepared from solutions
By (Dow Chemical (DowChemical, Midland, MI)) that derives from available is dissolved among the 140.08 gram PGMEA preparation photo-acid agent (PAG) solution with 60.02 gram UVI-6976.
Embodiment 4
The terpolymer of Comparative Examples 10 is synthetic
By 168.0 gram styrene (are derived from (Aldrich of A Deruiqi company of Milwaukee, the state of Wisconsin, Milwaukee, WI)), 84.0 gram vinyl cyanide (deriving from the A Deruiqi company of Milwaukee, the state of Wisconsin), 28.3 gram glycidyl methacrylate (deriving from the A Deruiqi company of Milwaukee, the state of Wisconsin) and 7.0 gram dicumyl peroxides (deriving from the A Deruiqi company of Milwaukee, the state of Wisconsin) are dissolved among the 1120 gram PGMEA preparation solution.Under magnetic agitation, in nitrogen, this solution is heated to 120 ℃.Polyreaction was carried out 28 hours at 120 ℃.Find that by solid analysis actual yield is 97.5% of a theoretical value.In isopropyl alcohol, precipitate terpolymer, filter, and in a vacuum with 50 ℃ of dried overnight.
Embodiment 5
The negative photoresist coating that comprises the epoxy phenol novolac resin
1. top coat formulations prepared from solutions
By 15.17 gram DEN 431 (the epoxy phenol novolac resin derives from the Dow Chemical (Dow Chemical, Midland MI) of Michigan's Midland) being dissolved in the potpourri of 59.57 gram PGMEA and 25.59 gram EAA preparation solution.Then 32.03 of preparation among the embodiment 2 being restrained the 2.52 gram PAG solution that prepare among copolymer solutions and the embodiment 3 is added in 15.53 these solution of gram.The top coat solution that stirring makes, and by the filtration of 0.1 micron film filtrator.
2. wafer patternization
In the mode that is similar to prior art nitride masking method but be to use composition of the present invention, with design transfer to silicon wafer.Specifically, be spin-coated on the silicon wafer with the rotating speed of the 1000rpm bottoming agent solution with preparation among the embodiment 1, the spin coating time is 1 minute.Cure wafer 1 minute with 110 ℃, cured wafer 1 minute with 280 ℃ then., cured 2 minutes with 110 ℃ then the top coat solution spin coating of preparation in the present embodiment part 11 minute with the rotating speed of 1500rpm.With imaging mode, with the dosage of 500 milli Jiao/square centimeters, expose to the sun with the ultraviolet light of 365 nanometers and to penetrate top coat, cured 2 minutes with 110 ℃ then.After curing, top coat is developed by use ethyl lactate with 200rpm, with 300rpm with isopropyl alcohol flushing 30 seconds, with 2000rpm Rotary drying 30 seconds.At last, cured wafer 5 minutes with 220 ℃.Obtain negative pattern (negative pattern).
3. etching test
The wafer 4 hours of patterning in the etching present embodiment part 2 in 75 ℃, 30%KOH aqueous solution then.Etching silicon in the zone that polymer coating of no use covers, the degree of depth is 165 microns, and the zone that has been coated with polymkeric substance is kept perfectly intact.Recessed cutting taken place hardly, and this can be determined by width that observe to measure the protective seam that etching area edge stretches out under confocal microscope.Find recessedly to be cut to 16.70 microns promptly 10.12% of etch depth.
Embodiment 6
The negative photoresist coating that comprises epoxy bisphenol-A/Bisphenol F resin
1. top coat formulations prepared from solutions
By (epoxy bisphenol-A/Bisphenol F resin, the Dow Chemical (Dow Chemical, Midland, MI)) that derives from available is dissolved in the potpourri of 59.74 gram PGMEA and 25.39 gram EAA preparation solution with 15.02 gram DER 353.Then 32.00 of preparation among the embodiment 2 being restrained the 2.52 gram PAG solution that prepare among copolymer solutions and the embodiment 3 is added in 15.50 these solution of gram.The top coat solution that stirring makes, and by the filtration of 0.1 micron film filtrator.
2. wafer patternization
In the mode that is similar to prior art nitride masking method but be to use composition of the present invention, with design transfer to silicon wafer.Specifically, with 1000rpm the bottoming agent solution of preparation among the embodiment 1 is spin-coated on the silicon wafer, the spin coating time is 1 minute.Cured 1 minute with 110 ℃, cured 1 minute with 280 ℃ then.With 1500rpm the top coat solution for preparing in the present embodiment part 1 is spin-coated on the prime coat top then, the spin coating time is 1 minute, cures 2 minutes with 110 ℃.With imaging mode, with the dosage of 500 milli Jiao/square centimeters, expose to the sun with the ultraviolet light of 365 nanometers and to penetrate top coat, cured 2 minutes with 110 ℃ then.After curing, top coat is developed by use ethyl lactate with 200rpm, with 300rpm with isopropyl alcohol flushing 30 seconds, with 2000rpm Rotary drying 30 seconds.At last, cured wafer 5 minutes with 220 ℃.Obtain negative pattern.
3. etching test
Be etched in the wafer 4 hours of patterning in the present embodiment part 2 with 75 ℃, 30%KOH aqueous solution.Etching silicon in the zone that polymer coating of no use covers, the degree of depth is 165 microns.The zone that has been coated with polymkeric substance is kept perfectly intact.Recessed cutting almost do not taken place, and this can determine by the width of measuring the protective seam that etching area edge stretches out with the confocal microscopy sem observation.Find recessedly to be cut to 16.74 microns promptly 10.14% of etch depth.
Embodiment 7
The negative photoresist coating that comprises the cresol novolac epoxy varnish gum
1. top coat formulations prepared from solutions
(the cresol novolac epoxy varnish gum, the vapour Ba Jirui company (Ciba Geigy, Tarrytown, NY)) that derives from New York, United States Ta Lidun is dissolved in the potpourri of 119.07 gram PGMEA and 51.03 gram EAA preparation solution with 30.01 gram ECN 1299.Then 32.06 of preparation among the embodiment 2 being restrained the 2.52 gram PAG solution that prepare among copolymer solutions and the embodiment 3 is added in 15.51 these solution of gram.The top coat solution that stirring makes, and by the filtration of 0.1 micron film filtrator.
2. wafer patternization
With 1000rpm the bottoming agent solution of preparation among the embodiment 1 is spin-coated on the silicon wafer, the spin coating time is 1 minute.Cured 1 minute with 110 ℃, cured 1 minute with 280 ℃ then.With 1500rpm the top coat solution for preparing in the present embodiment part 1 is spin-coated on the prime coat top, the spin coating time is 1 minute, cures 2 minutes with 110 ℃.With imaging mode, with the dosage of 500 milli Jiao/square centimeters, expose to the sun with the ultraviolet light of 365 nanometers and to penetrate top coat, cured 2 minutes with 110 ℃ then.After curing, top coat is developed by use ethyl lactate with 200rpm, with 300rpm with isopropyl alcohol flushing 30 seconds, with 2000rpm Rotary drying 30 seconds.At last, cured wafer 5 minutes with 220 ℃.Obtain negative pattern.
3. etching test
In the mode that is similar to prior art nitride masking method but be to use composition of the present invention, with design transfer to silicon wafer.Specifically, with the wafer of patterning in 75 ℃, 30%KOH aqueous solution etching present embodiment part 24 hours.Etching silicon in the zone that polymer coating of no use covers, the degree of depth is 165 microns.The zone that has been coated with polymkeric substance is kept perfectly intact.Recessed cutting almost do not taken place, and this can determine by the width of measuring the protective seam that etching area edge stretches out with the confocal microscopy sem observation.Find recessedly to be cut to 23.96 microns promptly 14.52% of etch depth.
Embodiment 8
The negative photoresist coating that comprises the epoxy bisphenol a resin
1. top coat formulations prepared from solutions
By (the epoxy bisphenol a resin, the Dow Chemical (Dow Chemical, Midland, MI)) that derives from available is dissolved in the potpourri of 59.52 gram PGMEA and 25.53 gram EAA preparation solution with 15.04 gram Epon 825.Then, 32.08 of preparation among the embodiment 2 being restrained the 2.52 gram PAG solution that prepare among copolymer solutions and the embodiment 3 is added in 15.53 these solution of gram.The top coat solution that stirring makes, and by the filtration of 0.1 micron film filtrator.
2. wafer patternization
With 1000rpm the bottoming agent solution of preparation among the embodiment 1 is spin-coated on the silicon wafer, the spin coating time is 1 minute.Cured 1 minute with 110 ℃, cured 1 minute with 280 ℃ then.With 1500rpm the top coat solution for preparing in the present embodiment part 1 is spin-coated on the prime coat top, the spin coating time is 1 minute, cures 2 minutes with 110 ℃.With imaging mode, with the dosage of 500 milli Jiao/square centimeters, expose to the sun with the ultraviolet light of 365 nanometers and to penetrate top coat, cured 2 minutes with 110 ℃ then.After curing, top coat is developed by use ethyl lactate with 200rpm, with 300rpm with isopropyl alcohol flushing 30 seconds, with 2000rpm Rotary drying 30 seconds.At last, cured wafer 5 minutes with 220 ℃.Obtain negative pattern.
3. etching test
In the mode that is similar to prior art nitride masking method but be to use composition of the present invention, with design transfer to silicon wafer.Specifically, with the wafer of patterning in 75 ℃, 30%KOH aqueous solution etching present embodiment part 24 hours.Etching silicon in the zone that polymer coating of no use covers, the degree of depth is 165 microns.The zone that has been coated with polymkeric substance is kept perfectly intact.Recessed cutting almost do not taken place, and this can determine by the width of measuring the protective seam that etching area edge stretches out with the confocal microscopy sem observation.Find recessedly to be cut to 16.04 microns promptly 9.72% of etch depth.
Embodiment 9
The negative photoresist coating that comprises epoxy bisphenol-A phenolic varnish gum
1. top coat formulations prepared from solutions
By (epoxy bisphenol-A phenolic varnish gum, the Dow Chemical (Dow Chemical, Midland, MI)) that derives from available is dissolved in the potpourri of 59.51 gram PGMEA and 25.52 gram EAA preparation solution with 15.07 gram Epon SU-8.Then 32.00 of preparation among the embodiment 2 is restrained the 2.50 gram PAG solution that prepare among copolymer solutions and the embodiment 3 and be added into 15.50 these solution of gram.The top coat solution that stirring makes, and by the filtration of 0.1 micron film filtrator.
2. wafer patternization
With 1000rpm the bottoming agent solution of preparation among the embodiment 1 is spin-coated on the silicon wafer, the spin coating time is 1 minute.Cured 1 minute with 110 ℃, cured 1 minute with 280 ℃ then.With 1500rpm the top coat solution for preparing in the present embodiment part 1 is spin-coated on the prime coat top, the spin coating time is 1 minute, cures 2 minutes with 110 ℃.With imaging mode, with the dosage of 500 milli Jiao/square centimeters, expose to the sun with the ultraviolet light of 365 nanometers and to penetrate top coat, cured 2 minutes with 110 ℃ then.After curing, top coat is developed by use ethyl lactate with 200rpm, with 300rpm with isopropyl alcohol flushing 30 seconds, with 2000rpm Rotary drying 30 seconds.At last, cured wafer 5 minutes with 220 ℃.Obtain negative pattern.
3. etching test
In the mode that is similar to prior art nitride masking method but be to use composition of the present invention, with design transfer to silicon wafer.Specifically, with the wafer of patterning in 75 ℃, 30%KOH aqueous solution etching present embodiment part 24 hours.Etching silicon in the zone that does not have the overlie polymer coating, the degree of depth are 165 microns.The zone that has been coated with polymkeric substance is kept perfectly intact.Recessed cutting almost do not taken place, and this can determine by the width of measuring the protective seam that etching area edge stretches out with the confocal microscopy sem observation.Find recessedly to be cut to 22.32 microns promptly 13.53% of etch depth.
Comparative Examples
The negative photoresist coating that comprises terpolymer
1. top coat formulations prepared from solutions
Be dissolved in the potpourri of 140.05 gram PGMEA and 40.00 gram EAA preparation solution by 32.05 gram terpolymers with preparation among the embodiment 4.Then 4.52 gram UVI-6976 are added into this solution.The top coat solution that stirring makes filters by 0.1 micron film filtrator.
2. wafer patternization
With 1000rpm the bottoming agent solution of preparation among the embodiment 1 is spin-coated on the silicon wafer, the spin coating time is 1 minute.Cured 1 minute with 110 ℃, cured 1 minute with 280 ℃ then.With 1500rpm the top coat solution for preparing in the present embodiment part 1 is spin-coated on the prime coat top, the spin coating time is 1 minute, cures 2 minutes with 110 ℃.With imaging mode, with the dosage of 500 milli Jiao/square centimeters, expose to the sun with the ultraviolet light of 365 nanometers and to penetrate top coat, cured 2 minutes with 110 ℃ then.After curing, top coat is developed by use ethyl lactate with 200rpm, with 300rpm with isopropyl alcohol flushing 30 seconds, with 2000rpm Rotary drying 30 seconds.At last, cured wafer 5 minutes with 220 ℃.Obtain negative pattern.
3. etching test
In the mode that is similar to prior art nitride masking method with design transfer to silicon wafer.Specifically, with the wafer of patterning in 75 ℃, 30%KOH aqueous solution etching present embodiment part 24 hours.Etching silicon in the zone that does not have the overlie polymer coating, the degree of depth are 160 microns.The zone that has been coated with polymkeric substance is kept perfectly intact.Determine recessed cutting by the width of measuring the protective seam that etching area edge stretches out with the confocal microscopy sem observation.Find recessedly to be cut to 65.78 microns promptly 41.11% of etch depth.
Claims (39)
1. photosensitive composition that can be used as protective seam, described composition comprise dissolving or are dispersed in first polymkeric substance, second polymkeric substance and photo-acid agent in the dicyandiamide solution, wherein:
Described first polymkeric substance comprises:
Wherein:
Each R
1Be independently selected from hydrogen and C
1-C
8Alkyl;
Each R
2Be independently selected from hydrogen, C
1-C
8Alkyl and C
1-C
8Alkoxy;
Described second polymkeric substance comprises the repeated monomer that contains epoxide group.
2. composition as claimed in claim 1 is characterized in that, described second polymkeric substance also comprises the repeated monomer that contains phenolic group.
3. composition as claimed in claim 1 is characterized in that, described second polymkeric substance is selected from epoxy phenol novolac resin, epoxy bisphenol-A/F resin, cresol novolac epoxy varnish gum, epoxy bisphenol a resin and epoxy bisphenol-A phenolic varnish gum.
4. composition as claimed in claim 1 is characterized in that, described photo-acid agent is selected from hexafluoro-antimonic acid triaryl matte, hexafluorophosphoric acid triaryl matte, hexafluoro-antimonic acid diaryl iodine, hexafluorophosphoric acid diaryl iodine,
Each R wherein
3Be independently selected from C
3H
7, C
8H
17, CH
3C
6H
4, and camphor.
5. composition as claimed in claim 1 is characterized in that, is the benchmark of 100 weight % in the general assembly (TW) of described polymkeric substance, and described polymkeric substance comprises (I) of about 50-90 weight % and (II) of about 10-50 weight %.
6. method that forms microelectronic structure, described method comprises:
Microelectronic substrates is provided;
Apply prime coat to described base material, described prime coat comprises the silane that is dispersed or dissolved in the dicyandiamide solution;
Apply photosensitive layer to described prime coat, described photosensitive layer comprises photo-acid agent, first polymkeric substance and second polymkeric substance that is dispersed or dissolved in the dicyandiamide solution, wherein:
Described first polymkeric substance comprises:
Wherein:
Each R
1Be independently selected from hydrogen and C
1-C
8Alkyl;
Each R
2Be independently selected from hydrogen, C
1-C
8Alkyl and C
1-C
8Alkoxy;
Described second polymkeric substance comprises the repeated monomer that contains epoxide group.
7. method as claimed in claim 6 is characterized in that, described second polymkeric substance also comprises the repeated monomer that contains phenolic group.
8. method as claimed in claim 6 is characterized in that, described second polymkeric substance is selected from epoxy phenol novolac resin, epoxy bisphenol-A/F resin, cresol novolac epoxy varnish gum, epoxy bisphenol a resin and epoxy bisphenol-A phenolic varnish gum.
9. method as claimed in claim 6 is characterized in that, described photo-acid agent is selected from hexafluoro-antimonic acid triaryl matte, hexafluorophosphoric acid triaryl matte, hexafluoro-antimonic acid diaryl iodine, hexafluorophosphoric acid diaryl iodine,
Each R wherein
3Be independently selected from C
3H
7, C
8H
17, CH
3C
6H
4, and camphor.
10. method as claimed in claim 6 is characterized in that, is the benchmark of 100 weight % in the general assembly (TW) of described polymkeric substance, and described polymkeric substance comprises (I) of about 50-90 weight % and (II) of about 10-50 weight %.
11. method as claimed in claim 6 is characterized in that, described silane has and is selected from following general formula:
Wherein:
Each i, j and k are independently selected from 0 and 1, if among i and the j is 1, then another is 0;
Each R
4Be independently selected from hydrogen, halogen, C
1-C
8Alkyl, C
1-C
8Alkoxy, C
1-C
8Haloalkyl, amino and C
1-C
8Alkyl amino;
Each R
5Be independently selected from C
1-C
8Aliphatic group;
Each R
6Be independently selected from hydrogen and haloalkyl;
Each X is independently selected from halogen, hydroxyl, C
1-C
4Alkoxy and C
1-C
4Carboxyl;
Y is selected from oxygen and sulphur;
Z is selected from nitrogen and phosphorus;
Each d is independently selected from 0 and 1; And
Wherein:
Each R
7Be independently selected from hydrogen, halogen, C
1-C
8Alkyl, C
1-C
8Alkoxy, C
1-C
8Haloalkyl, amino and C
1-C
8Alkyl amino;
Each R
8Be independently selected from C
1-C
8Aliphatic group.
12. method as claimed in claim 6 is characterized in that, described silane is selected from aminoalkoxy silane, phenyl silane and diphenyl silane.
13. method as claimed in claim 12 is characterized in that, described silane is selected from aminoalkyl alkoxy silane and phenyl amino alkylalkoxy silane.
14. method as claimed in claim 12, it is characterized in that, described silane is selected from TSL 8330, aminopropyltriethoxywerene werene, N-phenyl amino propyl trimethoxy silicane, N-phenyl amino propyl-triethoxysilicane, the 3-glycidoxypropyltrime,hoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-sulfydryl propyl group-trimethoxy silane, phenyltrimethoxysila,e, phenyl trichlorosilane, phenyl triethoxysilane, the phenyl triacetoxysilane, dimethoxydiphenylsilane, diphenyl dichlorosilane, diphenyl silanodiol, 2-phenylethyl trialkoxy silane, right/-the chlorphenyl trimethoxy silane, right/-the bromophenyl trimethoxy silane, (right/-chloromethyl) phenyltrimethoxysila,e, 2-(right/-methoxyl) the phenylethyl trimethoxy silane, 2-(right/-chloromethyl) the phenylethyl trimethoxy silane, 3,4-dichlorophenyl trichlorosilane, 3-phenoxy propyl trichlorosilane, 3-(N-phenyl amino) propyl trimethoxy silicane, and 2-(diphenylphosphino) ethyl triethoxysilane.
15. method as claimed in claim 6 is characterized in that, also is included in to apply to cure described prime coat after the described prime coat.
16. method as claimed in claim 15 is characterized in that, described prime coat also comprises catalyzer, and described prime coat baking step causes described crosslinked with silicane.
17. method as claimed in claim 6 is characterized in that, also is included in to apply to cure described photosensitive layer after the described photosensitive layer.
18. method as claimed in claim 17 is characterized in that, described baking step causes the silane covalent bond of at least a described polymkeric substance and the described prime coat of described photosensitive layer.
19. method as claimed in claim 6 is characterized in that, also comprising exposes to the sun with actinic radiation penetrates the first of described photosensitive layer, and the second portion of described photosensitive layer exposes to the sun without actinic radiation and penetrates.
20. method as claimed in claim 19 is characterized in that, also being included in exposes to the sun with actinic radiation cures described photosensitive layer after penetrating.
21. method as claimed in claim 20 is characterized in that, the described first of described photosensitive layer is crosslinked during described curing.
22. method as claimed in claim 20 is characterized in that, also comprises described photosensitive layer is developed.
23. method as claimed in claim 22 is characterized in that, described development step causes the second portion of described photosensitive layer to be removed substantially during described development step, comprises the stacked of the photosensitive layer that wherein formed pattern thereby form.
24. method as claimed in claim 23 is characterized in that, also is included in described development step and cures described photosensitive layer afterwards.
25. method as claimed in claim 23 is characterized in that, comprises that also etching is described stacked, thus with the design transfer of described photosensitive layer to described base material.
26. method as claimed in claim 25 is characterized in that, described photosensitive layer shows recessed the cutting less than about 20% after described etching step.
27. method as claimed in claim 25 is characterized in that, the pinhole number that every square centimeter of base material of described photosensitive layer shows is less than about 0.1.
28. method as claimed in claim 6 is characterized in that, described base material is selected from Si base material, SiO
2Base material, Si
3N
4Base material, SiO
2/ Si base material, Si
3N
4/ Si base material, glass baseplate, quartz substrate, ceramic base material, semiconductor substrate and metal base.
29. a microelectronic structure, it comprises:
Microelectronic substrates;
With the prime coat of described base material adjacent, described prime coat comprises crosslinked silane;
The photosensitive layer adjacent with described prime coat, described photosensitive layer comprises:
First polymkeric substance, it comprises:
Wherein:
Each R
1Be independently selected from hydrogen and C
1-C
8Alkyl;
Each R
2Be independently selected from hydrogen, C
1-C
8Alkyl and C
1-C
8Alkoxy;
Second polymkeric substance, it comprises the repeated monomer that contains crosslinked epoxide group.
30. microelectronic structure as claimed in claim 29 is characterized in that, described second polymkeric substance also comprises the repeated monomer that contains phenolic group.
31. microelectronic structure as claimed in claim 29, it is characterized in that described second polymkeric substance is selected from epoxy phenol novolac resin, epoxy bisphenol-A/F resin, cresol novolac epoxy varnish gum, epoxy bisphenol a resin and epoxy bisphenol-A phenolic varnish gum.
32. microelectronic structure as claimed in claim 29 is characterized in that, described silane comprises amine, and second polymkeric substance of described photosensitive layer comprises and the covalently bound epoxide group of described amine.
33. microelectronic structure as claimed in claim 29 is characterized in that, is the benchmark of 100 weight % in the general assembly (TW) of described polymkeric substance, described polymkeric substance comprises (I) of about 50-90 weight % and (II) of about 10-50 weight %.
34. microelectronic structure as claimed in claim 29 is characterized in that, described silane has and is selected from following general formula:
Wherein:
Each i, j and k are independently selected from 0 and 1, if among i and the j is 1, then another is 0;
Each R
4Be independently selected from hydrogen, halogen, C
1-C
8Alkyl, C
1-C
8Alkoxy, C
1-C
8Haloalkyl, amino and C
1-C
8Alkyl amino;
Each R
5Be independently selected from C
1-C
8Aliphatic group;
Each R
6Be independently selected from hydrogen and haloalkyl;
Each X is independently selected from halogen, hydroxyl, C
1-C
4Alkoxy and C
1-C
4Carboxyl;
Y is selected from oxygen and sulphur;
Z is selected from nitrogen and phosphorus;
Each d is independently selected from 0 and 1; And
Wherein:
Each R
7Be independently selected from hydrogen, halogen, C
1-C
8Alkyl, C
1-C
8Alkoxy, C
1-C
8Haloalkyl, amino and C
1-C
8Alkyl amino;
Each R
8Be independently selected from C
1-C
8Aliphatic group.
35. microelectronic structure as claimed in claim 29 is characterized in that, described silane is selected from aminoalkoxy silane, phenyl silane and diphenyl silane.
36. microelectronic structure as claimed in claim 35 is characterized in that, described silane is selected from aminoalkyl alkoxy silane and phenyl amino alkylalkoxy silane.
37. microelectronic structure as claimed in claim 35, it is characterized in that, described silane is selected from TSL 8330, aminopropyltriethoxywerene werene, N-phenyl amino propyl trimethoxy silicane, N-phenyl amino propyl-triethoxysilicane, the 3-glycidoxypropyltrime,hoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-sulfydryl propyl group-trimethoxy silane, phenyltrimethoxysila,e, phenyl trichlorosilane, phenyl triethoxysilane, the phenyl triacetoxysilane, dimethoxydiphenylsilane, diphenyl dichlorosilane, diphenyl silanodiol, 2-phenylethyl trialkoxy silane, right/-the chlorphenyl trimethoxy silane, right/-the bromophenyl trimethoxy silane, (right/-chloromethyl) phenyltrimethoxysila,e, 2-(right/-methoxyl) the phenylethyl trimethoxy silane, 2-(right/-chloromethyl) the phenylethyl trimethoxy silane, 3,4-dichlorophenyl trichlorosilane, 3-phenoxy propyl trichlorosilane, 3-(N-phenyl amino) propyl trimethoxy silicane, and 2-(diphenylphosphino) ethyl triethoxysilane.
38. microelectronic structure as claimed in claim 29 is characterized in that, described base material is selected from Si base material, SiO
2Base material, Si
3N
4Base material, SiO
2/ Si base material, Si
3N
4/ Si base material, glass baseplate, quartz substrate, ceramic base material, semiconductor substrate and metal base.
39. microelectronic structure as claimed in claim 29 is characterized in that, described crosslinked epoxide group has following formula:
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/736,429 US7709178B2 (en) | 2007-04-17 | 2007-04-17 | Alkaline-resistant negative photoresist for silicon wet-etch without silicon nitride |
| US11/736,429 | 2007-04-17 | ||
| PCT/US2008/054885 WO2008127785A1 (en) | 2007-04-17 | 2008-02-25 | Alkaline-resistant negative photoresist for silicon wet-etch without silicon nitride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101657758A true CN101657758A (en) | 2010-02-24 |
| CN101657758B CN101657758B (en) | 2015-03-04 |
Family
ID=39864285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880012312.7A Active CN101657758B (en) | 2007-04-17 | 2008-02-25 | Alkaline-resistant negative photoresist for silicon wet-etch without silicon nitride |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US7709178B2 (en) |
| EP (1) | EP2142960B1 (en) |
| JP (1) | JP5017449B2 (en) |
| KR (1) | KR101425697B1 (en) |
| CN (1) | CN101657758B (en) |
| AT (1) | ATE541240T1 (en) |
| TW (1) | TWI436164B (en) |
| WO (1) | WO2008127785A1 (en) |
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| CN111176070A (en) * | 2018-11-12 | 2020-05-19 | 台湾永光化学工业股份有限公司 | Negative photoresist composition and use thereof |
| CN113518817A (en) * | 2019-03-06 | 2021-10-19 | 荣昌化学制品株式会社 | Silicon nitride film etching composition |
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| US8192642B2 (en) * | 2007-09-13 | 2012-06-05 | Brewer Science Inc. | Spin-on protective coatings for wet-etch processing of microelectronic substrates |
| US9402138B2 (en) | 2012-10-12 | 2016-07-26 | Infineon Technologies Ag | MEMS device and method of manufacturing a MEMS device |
| US9299778B2 (en) | 2012-11-08 | 2016-03-29 | Brewer Science Inc. | CVD-free, scalable processes for the production of silicon micro- and nanostructures |
| TWI597574B (en) * | 2015-08-19 | 2017-09-01 | 奇美實業股份有限公司 | Photosensitive resin composition and application thereof |
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2007
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111176070A (en) * | 2018-11-12 | 2020-05-19 | 台湾永光化学工业股份有限公司 | Negative photoresist composition and use thereof |
| CN111176070B (en) * | 2018-11-12 | 2023-09-01 | 台湾永光化学工业股份有限公司 | Negative photoresist composition and use thereof |
| CN113518817A (en) * | 2019-03-06 | 2021-10-19 | 荣昌化学制品株式会社 | Silicon nitride film etching composition |
| CN113518817B (en) * | 2019-03-06 | 2022-08-16 | 荣昌化学制品株式会社 | Silicon nitride film etching composition |
Also Published As
| Publication number | Publication date |
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| ATE541240T1 (en) | 2012-01-15 |
| KR20100016582A (en) | 2010-02-12 |
| WO2008127785A1 (en) | 2008-10-23 |
| US7709178B2 (en) | 2010-05-04 |
| KR101425697B1 (en) | 2014-08-01 |
| TW200900860A (en) | 2009-01-01 |
| JP2010525398A (en) | 2010-07-22 |
| CN101657758B (en) | 2015-03-04 |
| JP5017449B2 (en) | 2012-09-05 |
| US20080261145A1 (en) | 2008-10-23 |
| EP2142960A4 (en) | 2010-11-10 |
| EP2142960B1 (en) | 2012-01-11 |
| EP2142960A1 (en) | 2010-01-13 |
| TWI436164B (en) | 2014-05-01 |
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